Method of improving the properties of organic polymeric material



United States Patent 3,547,666 METHOD OF IMPROVING THE PROPERTIES OFORGANIC POLYMERIC MATERIAL William G. London, Erwinua, Pa. 18920 NoDrawing. Original application Mar. 18, 1963, Ser. No. 266,080, nowPatent No. 3,379,709, dated Apr. 23, 1968. Divided and this applicationAug. 31, 1967, Ser. No. 664,651

Int. Cl. C08b 27/00, 45/00; C08c 11/34 U.S. Cl. 106-171 7 ClaimsABSTRACT OF THE DISCLOSURE A water insoluble, organo-chromium complexcomprising a fused chromium-monocarboxylic organic acid coordinationcompound, prepared by melting together a trivalent chromium salt and amonocarboxylic organic acid, bonded to n-butanol or an aliphatic alcoholcontaining from to 18 carbon atoms, is mixed with a polymeric organicmaterial.

This application is a division of copending application Ser. No.266,080, filed Mar. 18, 1963, now Patent No. 3,379,709.

The present invention relates to a method for producing organo-metalcompositions, to the compositions produced thereby, and to highmolecular weight organic substances modified by said compositions.

Coordination compounds of metals such as chromium and organic acids areWell known in the art and are de scribed, for example, in US. PatentsNos. 2,273,040, 2,356,161, 2,524,803 and 2,683,156 to Iler. While theprecise structure of these compounds has not been fully elucidated, theyare usually classed as Werner complexes. In general the ratio ofcarboxylic acid to metal atoms in such compounds is less than mighttheoretically have been considered possible, if the metal, e.g.chromium, is assumed to have a coordination number of six, and thesecomplexes can therefore be considered starved in that the capacity ofthe metal to form coordinate bonds is not fully utilized.

The coordination compounds or complexes just described have been used ina variety of ways, for example, in adhesives and in water proofingcompositions. In some cases they have been employed in solutions oflower aliphatic alcohols, e.g. methanol or ethanol. However, in theseinstances it is clear that the alcohol is merely a vehicle and has norole in determining the properties of the complex.

It has now been discovered that novel metal-organo compositions can bemade by mixing a solid metalorganic acid coordination compound with analcohol having at least four carbon atoms at at least 80 C., andpreferably at the boiling point (standard pressure) of the alcohol.

Although the exact structure of the novel compositions has not beenprecisely determined, it is clear that they represent something morethan merely a solution of the metal-acid coordination compound in thealcohol since the properties of the alcohol-containing compositions arequite different from those of the coordination compound. While I do notintend to be limited to any structural theory, I consider it likely thatthe alcohols fill, in whole or in part, the potential coordinationvalences of the previously starved complex, in effect creating a newcomplex.

The novel compositions can be used in a great variety of differentapplications. In general they are incorporated in various organicmaterials where they function to change the surface properties of thematerial. The way in which the novel complexes affect the surfaceproperties of these ice materials can be controlled by the choice ofalcohol used in the composition. Among other fields in which the novelcompositions find employment there may be mentioned the preparation ofadhesives and adhesive products, including self-adhesive labels andmasking tape, the compounding of rubber for use in automobile tires andelsewhere, and the formulation of polyalkylene, e.g. polyethylene,products to make such products receptive to adhesives.

In one aspect the invention therefore comprises a method for makingorgano-metal compositions comprising mixing a complex or coordinationcompound of a metal selected from the group consisting of chromium,titanium, zirconium and vanadium and an organic acid, with an alcoholhaving at least four carbon atoms at a temperture of at least C.

In its product aspects the invention includes a composition comprising acomplex or coordination compound of the metals referred to with anorganic acid, and an alcohol having at least 4 carbon atoms.

It has been found that the introduction of rosin into the compositionsaccording to the invention gives particularly useful results. In someinstances the rosin may be reacted directly with the metal component. Inanother variation the rosin may be added with the alcohol to a complexalready formed from a metal component and an organic acid other thanrosin. In the case of rosin compositions it is found that alcoholshaving 3 and more carbon atoms may be used to advantage.

The invention thus further includes a process for making metal-organocompositions which comprises forming a rosin containing organic acidcoordination compound with a metal of the class referred to and mixingsaid coordination compound with an aliphatic alcohol having at least 3carbon atoms at a temperature of at least 80 C.

From a product viewpoint, this aspect of the invention comprisescompositions of a metal-organic acid complex including a rosin; and analiphatic alcohol having at least 3 carbon atoms.

In yet another aspect the invention includes the process of modifyingvarious organic materials of high molecular weight by incorporating insuch materials the compositions described above, as well as thecomposite materials resulting from such incorporation.

THE ORGANO-METAL COMPOSITION As noted above, in its simplest aspect theinvention comprises compositions including an organic acid metalcoordination compound and an aliphatic alcohol having at least 4 carbonatoms.

The metal-organic acid coordination compounds or complexes can be madein various ways known to the art. However, preferably they are made byfusing an organic acid. (having at least 4 carbon atoms) with a metalsalt. Indeed it is one of the advantages of the present invention thatit makes the use of such fused coordination compounds practical.Coordination compounds made by fusion are inherently more desirable thanthose made by other methods because no extraneous reagents areintroduced. However, fusion products have been thought to be of verylimited solubility in most of the organic materials with whichcoordination compounds are normally used, presumably because in thefusion process a kind of polymerization seems to take place to createhigh molecular weight materials. For this reason the fusion productshave not been widely used. With the present invention, on the otherhand, a very large proportion of the fused compound is solubilized bythe aliphatic alcohol and the resulting composition itself has a veryhigh solubility in many organic materials; or can be made to have suchsolubility by a suitable choice of alcohol. Specifically it is foundthat when the alcohol has four or more car- 3 bon atoms there is a verysignificant increase in the amount of complex that can be dissolved anda change in the properties of the solution.

The metals which are suitable for use in the present invention includechromium, titanium, zirconium and vanadium. Of these chromium ispreferred. The form in which the metal is used in making themetal-organo complex is not especially significant; however, preferablyit is used as a salt or hydrated salt, the anionic component of which iscapable of being volatilized when the salt is fused with a carboxylicacid. Nitrates, halides and particularly hydrated halides are especiallyuseful. With chromium, for example, it is preferred to use hydratedchromic chloride [Cr(H O) ]Cl Alternatively, numerous salts containingchromium atoms capable of being converted to a valence state of threeare readily available and can be used. For example, as disclosed in US.Pat. 2,524,803, the hexavalent chromium atom in chromium trioxide can beconverted to a valence state of three by reduction with an alcohol priorto formation of an organo chromium coordination compound. Othercompounds such as hexavalent chromyl chloride can similarly be convertedand after conversion used as a source of trivalent chromium ions.

Numerous monobasic aliphatic carboxylic acids having at least fourcarbon atoms can be used in preparing the organo chromium coordinationcompounds including:

(a) Saturated straight chain acids, preferably having from 4 to 22carbon atoms such as butyric, valeric, caproic, lauric, myristic,palmitic, stearic, arachidic and docosanoic acids;

(b) Saturated branched chain acids such as iso-valeric, a-octyl-caproic,,B-ethyl-stearic and a-methyl caproic acids;

(c) Unsaturated acids (including branched and straight chain acids) suchas methacrylic, crotonic, sorbic, linoleic, geranic, oleic, palmitolicand eicosinic acids, and

(d) Aliphatic acids containing functional groups in addition to thecarboxylic groups, for example, halogenated acids such as a-ChlOrOvaleric acid and 5,5-dibromo caproic acid, hydroxy acids such asfl-hydroxy perlargonic acid and amino acids such as a-amino undecanoicacid.

Acids such as stearic, docosanoic, n-valeric, n-octanoic, crotonic andmethacrylic, iso-valeric, sorbic and linoleic acids are particularlypreferred. It is understood that the aliphatic carboxylic acid may beused in the form of an anhydride, a salt or an ester as well as a freeacid.

In making the metal-organic acid complex the specific proceduredescribed in Her 2,273,040 may be followed. Proceeding in this way themetal salt and the carboxylic acid are mixed in proportions such as togive a ratio of metal atoms to carboxylic acid groups of from say 1:4 to:1 and are then heated at temperatures sufiicient to reduce the metalsalt to a molten mass and to volatilize water and any acidic components(e.g. HCl) which may be released. Normally this will occur attemperatures over 100 C. and usually at say 120 C. to 250 C. The melt iskept at this temperature for say minutes to 4 hours and provision ismade to remove volatiles given off during the fusion. Thus, for example,if the chromium salt is chromium chloride hexahydrate [Cr(H O) ]Clhydrogen chloride is evolved and removed. The final product, uponcooling, is a glassy, rock-like mass. This may then be reduced to powderor granular form by grinding or crushing by conventional means such as aball mill or mortar and pestle.

After the metal-acid complex is formed, preferably as described above,and reduced to finely divided form, it is mixed with an alcohol havingat least four carbon atoms.

The alcohols in which the organo-metal coordination compounds aredissolved can be straight chain aliphatic alcohols such as n-butanol,n-pentanol, n-hexanol and cetyl alcohol; branched chain aliphaticalcohols such as tertiary butanol, isoamyl alcohol, isooctanol, and3-isopropyl-4-methyl-3-hexanol; and unsaturated alcohols such asl-penten-S-ol, 4-penten-2-ol and 5-hexen-3-ol. Polyhydric aliphaticalcohols having more than four carbon atoms, such as glycols, pinacolsand glycerols, i.e. trihydroxy aliphatic alcohols, can also be used.

In any case, the alcohol chosen is preferably a stable liquid at roomtemperature and will normally have a boiling point at atmosphericpressure of at least about C.

There is really no upper limit to the boiling point of the alcohol.Normally the alcohols most useful will be those boiling below about 300C.

The organo metal compositions are prepared by dissolving organo metalcoordination compound in the aliphatic alcohol at at least 80 C. andpreferably at about the boiling point of the alcohol. Preferably, thecompositions are prepared by refluxing the alcohol with the coordinationcompound at the boiling point of the alcohol for an extended period, sayfrom /2 hour up to several, say 4 hours. The proportions on a parts byweight basis, of alcohol to coordination compound can range from about1000:1 to about 0.1 to 1.0. Preferably the coordination compound isdissolved in the alcohol at atmospheric pressure; however, subandsuperatmospheric pressures can be employed. Agitation is preferablycarried out during heating and although refluxing is the preferred meansof agitating the mixture, other means such as stirring or bubbling gasthrough the solution are satisfactory.

It has been found that the metal-organo compositions of the inventionhave solubility characteristics significantly different from thesolubility properties of similar compositions prepared by knowntechniques. Moreover, it has been discovered that the solubilityproperties of these metal-organo compositions are unexpectedly relatedto the particular alcohols selected for refluxing. By means of thepresent invention the various advantages of producing metal-organic acidcoordination compounds by the fusion process may be obtained while thechief disadvantages, namely the insolubility of the fused product, isavoided. Moreover, since the solubility characteristics of the alcoholused have a pronounced effect upon the solubility characteristics of thecomposition, even though the organic acid remains the same, it ispossible to provide compositions containing a particular metal-organicacid coordination compound having a wide range of solubilitycharacteristics.

The unexpected solubility characteristics of the metalorganocompositions of the invention have not been observed except when themetal-organic acid coordination compound is combined with the alcohol atelevated temperature, usually approaching the boiling point of thealcohol, for a substantial period of time. This time will depend on thetemperature but will normally be at least 15 minutes. For example, whensamples of fused stearato chromic chloride are refluxed with an alcoholunder atmospheric pressure for 1 hour the amount of coordinationcompound which is dissolved is about four times greater than if thecomplex is merely put into the hot alcohol. The solubility of thealcoholic compositions in various organic solvents is also diiferent.Further it has been established that the particular alcohol employed inthe compositions of the invention has a pronounced effect upon theadhesive properties that these compositions impart to certain materials.

The metal-organic acid-alcohol compositions of the invention aregenerally stable solutions at room temperature. They have little or notendency to form sludges on storing. They can be added to a wide rangeof plastics, resins, natural and synthetic rubbers, natural andsynthetic gums, paraffins, microcrystalline waxes and the like orsolutions of these materials in organic solvents.

The novel process for preparing the organo chromium compositions and theproperties of these compositions will be illustrated in the followingExamples 1 to 8 which are to be considered illustrative. only and not aslimiting the scope of the invention.

In all examples in the specification, including Examples 1 to 8, fusingand refluxing are conducted at atmospheric pressure.

Example 1 illustrates the preparation of a fused organo chromiumcoordination compound comprising a trivalent chromium compound and analiphatic acid.

Example 1 Chromic chloride hexahydrate (42.6 g.) is mixed withdocosanoic acid (13.6 g.). The mixture is heated to a tem- 1 with n-amylalcohol for one hour are mixed with cc. of various solvents. Thisprocedure is repeated using 1 cc. samples of a composition made byrefluxing docosanato chromic chloride with tertiary butyl alcohol forone hour. After the samples have been allowed to stand at roomtemperature for 24 hours, they are inspected to determine whether therewas any phase separation or other indication of insolubility. Theresults of these observations are tabulated below:

TABLE II Docosanato Docosanato chromic chromic Tertchloride n-amylchloride butanol in tertalcohol in n-amyl Solvent control butanolcontrol alcohol White gasoline Insoluble Soluble Soluble. Carbontetrachloride Insoluble do ..do Do. Petroleum ether- Soluble do..." Do.Toluene do do..." Do. Isopropyl acetate do 0... .do Do. Isopropanol doSoluble ..do. Do. Water Insoluble .do Insoluble Insoluble.

perature of 150 C. and maintained at this temperature for one hour. Anair sweep is provided to remove volatile ingredients. The fused mass isallowed to cool to room temperature. A black, hard, rock-like mass, 46.8g., identified as the coordination compound, docosanato chromicchloride, is produced.

In the following example fused docosanato chromic chloride from Example1 is refluxed with various alcohols.

Example 2 A mixture of 20.4 g. of pulverized docosanato chromic chlorideproduced according to Example 1 and 105 g. of tertiary butyl alcohol isrefluxed for one hour at about 82.8 C. A second mixture comprising 20.1g. of the complex and 105 g. of n-amyl alcohol is refluxed for one hourat about 138 C. This procedure, using approximately 20.1 g. of thecomplex and 105 g. of the alcohol, is repeated with seven otheralcohols. In each case the mixture is refluxed at the boilingtemperature of the alcohol. The specific alcohols used are: methanol,ethanol, isopropanol, n-hexanol, stearyl alcohol, Oleyl alcohol and3-methyl-3- butyn-2-ol. In each case the complex remaining undissolvedis filtered out, air dried and-weighed. The results are as follows:

TABLE I Percent of total solids Alcohol: remaining undissolved Methanol40.9 Ethanol 32.7 Isopropanol 10.0 Tort-butanol 4.0 n-Amyl alcohol 8.7n-Hexanol 1 5.0 Stearyl alcohol 5 Oleyl alcohol 5 3-methyl-3-butyn-2-ol70 It is evident from the foregoing that the solubility of fusedcoordination compounds such as docosanato chromic chloride afterrefluxing in various alcohols varies widely depending upon theparticular alcohol employed.

It will also be observed that the ability of the alcohol to dissolve thecoordination compound tends to increase with increasing chain length ofthe alcohol and that a sharp increase in the ability appears to occurwith the four carbon alcohols.

The solubility in various solvents of decosan'ato chromic chloride,refluxed with n-amyl alcohol and with tertiary butyl alcohol (at 138 C.and 828 C. respectively) is illustrated in the following example.

Example 3 A series of 1 cc. samples of a composition made by refluxingdocosanato chromic chloride made as in Example It is apparent that thesolubility of tertiary butanol in various solvents is appreciablyafllected by the presence of the coordination compound. Moreover, thesolubility of fused docosanato chromic chloride refluxed in n-amylalcohol differs significantly from that of docosanato chromic chloriderefluxed in tertiary butanol. This is surprising since in priorinstances where organic acid chrome complexes were dissolved inalcohols, the nature of the alcohol was found to have little elfect onthe properties of the solution.

In the following example, a solution of docosanato chromic chloride inn-butanol is prepared according to the method described in U.S. Pat.2,524,803 to Iler, a method which does not involve fusion. This materialis compared with a fused docosanato chromic chloride compound which hasbeen refluxed with n-butanol according to the present invention.

Example 4 Ten grams of chromium trioxide crystals are dissolved in 19.2g. of 37% aqueous hydrochloric acid. After the chromium trioxide isdissolved, the solution is slowly added, dropwise, to 81.5 g. ofn-butanol, with occasional chilling to control the exothermic reaction.Docosanoic acid (17.0 g.) is added and the mixture refluxed for 30minutes. After standing at room temperature for 24 hours, an insolublegreen oil, docosanato chromic chloride, is noted on the bottom of thereaction vessel. Thus the nbutanol layer is saturated with docosanatochromic chloride.

A 20.4 g. sample of docosanato chromium chloride prepared according tothe procedure of Example 1 is then refluxed with g. of n-butanol for 1hour at about 118 C. according to the procedure of Example 2. 191.1 g.of-

in sealed test tubes for 24 hours. The results are tabulated below:

TABLE III Docosanato chromic chloride Fused docosanato prepared inchromium chloride n-butanol refluxed in Solvent (Iler process) n-butanolCarbon tetrachloride Insoluble Soluble. Petroleum ether do Do. Toluenedo Do. Isopropyl acetate- -.do Do. Isopropanol. S soluble. Do. WaterInsoluble- Insoluble. Hexane d Soluble.

The adhesion properties of the compositions described in Example 4 areillustrated in the following example.

Example The n-butanol solutions prepared in Example 4, i.e. then-butanol solution of docosanoic chromic chloride prepared by theprocess of Her 2,524,803 and the solution prethe diluted solutions,dried and tested for adhesion. Two series of tests were made. In onecommercial adhesive tape (Minnesota Mining and Manufacturing No. 202) isapplied at 400 p.s.i. and room temperature for two minutes and thenimmediately stripped off. In another, the

pared in accordance with the claimed processes are applied 5 mpg isallowed to remain for 7 days at and then to parchment. Specifically 2percent isopropanol solutions Stripped The results are tabulated below:

of each of the n-butanol solutions are prepared and super calenderedbrown vegetable parchment is dipped in the TABLE VI solutions, and driedfor 2 minutes at 104 C. A one inch stripping wide strip of pressuresensitive adhesive tape (Minnesota Initial force Mining and Mfg. Co. No.202) is then applied under a ggg gfgg g fig p ig g ggn g pressure of 400p.s.i. for 2 minutes at room temperature. chloride and Diluted with(g./in.) at 66 C.

The stripping force at 180 peelback is then me re in 975 1,050

in a standard tensile tester. The results are tabulated be- ISOpt opanol250 312 Tertiary butanol. 375 385 10W isopropanol 225 262 T L Imaternal: 3g;

Adhesion C m ition in isopropanol grams/inch in g./il10l1 2O3-mathy1-3-hutyn-20 1 250 425 Fused docosanato chromic chloride pre- 1Gross transfer of treatment to adhesive mass was noted.

pared by fusion process and refluxed in n-butanol 332 405 Metal-organiccomposltions contalnmg rosin Docosanato chromic chloride prepared innutano according to the Iler p 232 312 As noted above, the inventioncomprises compositions which contain rosin. These are of two types. Inone rosin From the foregoing it is evident that docosanato chromic isused alone as the Organic acid in h Organic id- 1 hl ri Prepared by thetwo different tech coordination compound. Alternatively, a metal-organicniq has different Solubility and releasing P P acid coordinationcompound formed without rosin can be In the following example, variousfused organochroheated i rosin d an l h L mium coordination Compoundsare P p and Subse- 3O Rosin containing compositions according to theinvenq y refluxed in certain alcohols- The Solubility Chartion are ofparticular use in modifying the adhesive characteristics of th smaterials are then ObSeTVedacteristics of various organic polymers, inparticular rub- Example 6 bers. It has, of course, been known to userosin itself to improve the adhesiveness of rubber. Compositions ac-FOUI' dlfferent organo'chromlum coordmatlon P cording to the inventionare, however, effective in much Pounds are Produced. accofding to themethoq desfznbed smaller quantities than rosin itself. Moreover, a largen EXamPIe 1 y .fuslngi of le acld and variety of effects can be obtainedusing the present comof ehromlc Chlonde hexahydrate, (11) of positionsby a suitable choice of alcohol. Many of such isovaleric acid and 21.3g. of chromic chloride hexahyeflects cannot be obtained using rosinitseli (irate, of Sorbie acid and 9 chromic In preparing the rosincontaining compositions accord- Ch r h hy and of llnolelc acid and ingto the invention, the general procedures outlined above 42.6 g. ofchromic chloride hexahydrate. Two samples are f n d That is to Say ametaporganic acid (each 20 of each 0f Compounds and plex is firstprepared, preferably by fusion. In preparing are t refluXed for one hourWith 100 8- Of tertiary the complex a salt of the metal to be used isfused with an butanol and I1-Pentan01 at the boiling Points of the 40organic acid in proportions of metal atoms to carboxylic SPeetiVe2110011015, using the technique of Example Simi acid groups ranging fromsay 1:6 to 10:1. If rosin is larly 28 25' Sample Of Product is refluxedfor one used in the fusion, it can be considered to be abietic acid,hour with isooctyl alco o for purposes of computing the proportions. Asin the To determine the Solubility characteristics of the resultspeciesof the invention disclosed earlier, the metal used ing liquids, 1Samples of each are mixed With 20 may be titanium, zirconium, chromiumor vanadium, with samples of various solvents and allowed to stand incorked h i preferred, Th t l i d, as b fo i th test tubes for 24 hours.form of a salt, preferably containing a volatilizable anion,

The results are tabulated below. such as chromium chloride hydrate.

TABLE V Percent Carbon Refiuxing insolublcs tetra- Petrole- IsopropylIso- Fused coordination compound alcohol present chloride um etherToluene acetate propanol Water Hexane Valerato chromic chloride 1 2.14S0lubl0 ..Insoluble Soluble Soluble. Soluble. Soluble.-. Insoluble.

Do 11-53331 .d0.... Soluble .do -do do Insoluble.. Soluble.

Isovalerato chromic chloride irlfianoi ....do Insoluble Slightly soluble..do ..do Soluble... Insoluble.

Do. n-g l ng l .do Soluble... Soluble .do ....do Insoluble Soluble.

Sorbato chromic chloride grtg n 25.5 Insoluble. Insoluble. Slightlysoluble do do Insoluble.

Do n-A in gli 7.7 Soluble..- Soluble--. Soluble .410 -.do Soluble.

Llnolasto chromic chloride ls ts l -4 ..-d0 do ..do Soluble do do Do.

1 After refluxing. 2 Negligible.

E mp 7 The organic acid used may be rosin itself or a mixture Samples ofthe organo chromium compositions whose preparation is described inExample 2, comprising docosanato chromic chloride dissolved in variousalcohols are further diluted to a 2% solids content with various solofrosin and an organic acid, preferably, but not necessarily, an organicacid having at least four carbon atoms. Any of the various types ofrosin generally available may be used, for example, gum rosin derivedfrom crude vents. Unbleached vegetable parchment is then dipped inturpentine, oleoresin, wood rosin and tall oil rosin. These are normallyconsidered to consist chiefly of resin acids of the abietic and pimarictype.

The organic acid used may include any of those previously referred to inconnection with the simple acidmetal coordination compounds referred toearlier in this specification. Similarly the detailed procedure used inpreparing the coordination compound is the same as that describedearlier, whether or not rosin is used in the organic acid component.

Following preparation of the acid-metal coordination compound, thatcompound is ground to powdered or granular form and then heated with analcohol having at least three carbon atoms in the molecule or, if norosin has been used in making the coordination compound, with both analcohol having at least three carbon atoms and with rosin. It will beunderstood, of course, that even if rosin has been used in preparing thecoordination compound, it may still be used with the alcohol in thesubsequent stage.

In yet another procedure, where rosin is used, a metal salt such aschromium chloride hexahydrate may be fused, by itself, to remove waterof hydration and then refluxed with a mixture of alcohol and rosin atthe boiling point of the mixture.

Generally at least one part by weight, and normally between about oneand about 20 parts by weight of alcohol are added per part of complex,assuming that rosin is present in the complex and none is to be addedwith the alcohol. If this is not the case, i.e. if rosin is to be addedwith the alcohol, between about one and about 20 parts of alcohol andbetween about 0.1 and about 2 parts of rosin are added, per part ofcomplex.

The manipulative techniques involved in dissolving the complex in thealcohol are very simple. The coordination compound is normally firstdissolved in the alcohol and the rosin is added. However, the rosin may,if desired, first be dissolved in the alcohol and the complex then addedto the solution. The alcohol must be at a temperature of at least 80 C.It is preferably at the boiling point and is maintained at the boilingpoint, or above, during the dissolution of the rosin and/or coordinationcompound. The coordination compound is preferably kept in contact withthe alcohol or alcohol-rosin solution, at the boiling point, andpreferably with agitation, for an extended time of at least fifteenminutes and often up to several, say 1 or 2 hours. Conveniently, as inthe case of the simple alcohol-complex compositions described earlier,the process is carried out by refluxing the coordination compound withalcohol or rosin-alcohol mixture.

In one variation of the invention, a particularly useful series ofcompositions can be formulated by adding to the metal-rosin-alcohol ormetal-acid-rosin-alcohol compositions a liquid paraifin or substitutedparaffin solvent. Examples of such solvents include pentane, hexane,heptane, trichloroethane and 1,1-dichloro-ethane. This can be doneconveniently by adding from say 1 to 100 parts by weight of the solvent,based on the weight of the basic coordination compound, to the alcoholor alcohol-rosin mixture, after the alcohol or alcohol mixture has beensubstantially saturated with complex and continuing the heating at theboiling point of the paralfin diluted mixture for several minutes, sayminutes to 60 minutes.

As indicated earlier, the rosin containing compositions just describedare soluble in a wide range of high molecular weight organic compounds.The solubility characteristics of any particular composition is relatedto the alcohol which it contains. It must be emphasized, however, thatthese unique characteristics are not obtained unless the rosin metal orrosin-acid-meta1 combinations are heated with the alcohol for a more orless extended time, in accordance with the invention.

The rosin containing compositions, their properties and preparations aredescribed in the following examples.

Example 8 Chromium chloride-hexahydrate (42.6 g.) is mixed withdocosanoic acid (13.6 g.) and the mixture heated until the temperaturereaches 180 C. A continuous air sweep is provided to remove volatiles.The mass is held at 180 C. for one hour. The resulting solid mass(approximately 42 g.) is ground to a powder and 20 g. of wood rosin and20 g. of isopropanol are added. The mixture is refluxed for 30 minutes.Hexane (175 g.) is then added and refluxing continued for another 30minutes. At the end of this time the solution is allowed to coolovernight. It is then filtered to remove 13.7 g. of solids. The filtratecontains 19.7% solids.

Example 9 of solids remain undissolved. Using no alcohol, 22.6 g.

of the solids remain undissolved.

Example 10 The procedure of Example 9 part (a) is repeated using talloil rosin in place of wood .rosin. The undissolved solids amount to 17.4g.

Example 11 Chromium chloride hexahydrate (42.6 g.) is mixed withoctanoic acid (23.0 g.) and the mixture is heated until the temperaturereaches C. The fused mass is held at 140 C. for one hour, at which timeits mass has decreased to 45.5 g. The coordination compound is thenground to a powder and 20 g. each of wood rosin and isopropanol areadded. The mixture is refluxed for 30 minutes. Hexane (170 g.) is thenadded and refluxing continued for another 30 minutes. The solution isallowed to stand overnight and then filtered. Insolubles amount to 7.2g. The solution contains 23.4% solids.

Example 12 The procedure of Example 11 is repeated substitutingisopropanol for hexane. No insolubles are left and the solution containsabout 25 solids.

Example 13 The procedure of Example 11 is repeated substitutingn-hexanol for both the isopropanol and the hexane. Again no insolublesare left and the filtrate contains about 25% solids.

Example 14- Chromic chloride hexahydrate (42.6 g.) is mixed with 33.6 g.of linoloic acid and the temperature of the mass is raised to C. Themass is held at this temperature for one hour after which 62.5 g. ofsolids remain. This is ground up and 20 g. each of gum rosin andisooctyl alcohol added. The mixture is refluxed for 30 minutes. Hexaneg.) is then added and the mixture refluxed for another 30 minutes. Thesolution is cooled overnight and filtered. Insolubles amount to 19.3 g.The solution contains about 25 solids.

Example 15 Chromium chloride hexahydrate (21.3 g.) is heated at 150 C.for one hour. An air sweep is provided to remove volatiles. The weightafter fusion is 15.3 g. To the fused material is added 10 g. gum rosinand 10 g. of isopropanol and the mixture is refluxed for 30 minutes.Hexane (85 g.) is then added and refluxing resumed for another 30minutes. The solution is allowed to cool overnight. The weight ofinsolubles is 32.9 g.

The foregoing example illustrates the fact that the alcohol in thepresent compositions enters into a combination with the metal and rosin,since in this experiment the weight of insolubles cannot be accountedfor solely on the basis of the formation of a chrome-rosin complex.

1 1 When this experiment is repeated, using n-butanol instead ofisopropanol, only 9.8 g. of insolubles are obtained. This illustratesthe eflect of changing the type of alcohol, in addition to rosin, in thecomposition.

Example 16 Chromic chloride hexahydrate (21.3 g.) is heated to 150 C.and held at that temperature under an air sweep for one hour. The weightafter fusion is 15.3 g. To this is added g. gum rosin and 10 g.isopropanol and the mixture is refluxed for 30 minutes. An additional100 g. isopropanol is then added and refluxing continued for 30 minutes.The solution is cooled overnight and then filtered. Insolubles amount to0.7 g.

Example 17 The procedure of Example 16 is repeated substitutingn-butanol for isopropanol. Insolubles are found to be 9.8 g.

Example 18 Chromic chloride hexahydrate (21.3 g.) is mixed with sorbicacid (12.4 g.), the mixture is heated to 130 C. and held at thattemperature, under an air sweep, for one hour. At the end of thisperiod, 10 g. of gum rosin and 10 g. of isopropanol are added andrefluxing continued for 30 minutes. N-amyl alcohol (85 g.) is added andrefluxing continued for 30 minutes. The insolubles amount to 4.3 g. Thesolution contains 23.35% solids.

Example 19 Chromium chloride hexahydrate (21.3 g.) is mixed with 6 gramsof crotonic acid, heated to 130 C. and maintained at that temperaturefor one hour. Gum rosin (10 g.) and isopropanol (10 g.) are then addedand refluxing carried out for 30 minutes. Isoamyl alcohol (85 g.) isthen added and the mixture refluxed for another 30 minutes. The amountof insolubles is negligible.

Example 20 The compound 12-hydroxy stearic acid (11.4 g.) is mixed with21.3 g. Cr(H O) Cl heated to 140 C. and maintained at that temperatureunder an air sweep for one hour. Gum rosin (10 g.) and isopropanol (10g.) are then added, and the mixture refluxed for 30 minutes.

' Hexane (85 g.) is added and refluxing continued for 30 minutes.Insolubles are about 10 g. The solution contains 21% solids.

Example 21 Chromium chloride hexahydrate (21.3 g.) is mixed with 11.4 g.of normal valeric acid. The temperature of the mass is raised to 120 C.,and the mass is held at 120-130 C. for one hour under an air sweep. Gumrosin (10 g.) and isopropanol (10 g.) are added and refluxed for 30minutes. Hexane (85 g.) is then added and refluxing resumed for 30minutes. There are no insolubles. Solids content of the solution is20.5%.

Example 22 Chromium chloride hexahydrate (21.3 g.) is mixed with 11.4 g.of isovaleric acid and the temperature of the mass is raised to 130 C.An air sweep is provided to remove volatile ingredients. The mass isheld at 130 C. for one hour. Gum rosin (10 g.) and isopropanol (10 g.)are added and refluxed for 30 minutes. Hexane (85 g.) is then added andrefluxing resumed for another 30 minutes. There are no insolubles.Solids content is 24.8%.

Example 23 Chromium chloride hexahydrate (21.3 g.) is mixed with 13.5 g.of isodecanoic acid and the temperature of the mass raised to 130 C. Anair sweep is provided to remove volatile ingredients. The mass is heldat 130 C. for one hour after which gum rosin (10 g.) and isopropanol (10g.) are added. The mixture is refluxed for 30 minutes, following whichhexane (85 g.) is added and 12 refluxing continued for another 30minutes. Insolubles are 10.5 g.

Example 24 Wood rosin (10 g.) is mixed with 6.8 g. of amino acetic acidand fused at 120 C. for 10 minutes. A yield of 16 g. of fusedrosin/amino acetic acid is obtained. Chromic chloride hexahydrate (21.3g.) is added to the fused mass and fusion continued at 120l30 C. for 25minutes. A yield of 30.1 grams of the chrome/rosin/ amino acetic complexis observed. Isopropanol g.) is added to the complex and the mixture isrefluxed for one hour. The insolubles are negligible.

Example 25 The procedure of Example 24 is repeated substitutingn-butanol for isopropanol. Insolubles amount to 22 g.

Example 26 Wood rosin (10 g.) is mixed with 10 grams of 2- aminooctanoic acid and fused for 10 minutes at C. A yield of 16.7 grams isobtained. Chromic chloride hexahydrate (21.3 g.) is added to the fusedmass and fusion resumed at 120-130" C. for one hour. A yield of 34.8 g.is obtained. Normal butanol (85 g.) is added and the mixture refluxedfor one hour. The insolubles are negligible.

HIGH MOLECULAR WEIGHT-ORGANIC MATE- RIALS CONTAINING THE METAL-ORGANICCOMPOSITIONS It has already been observed that the metal-organicacid-alcohol compositions, with or without rosin, whose preparation hasjust been described, may be used to great advantage to vary the surfaceproperties of various organic materials. It has, for example, beenobserved that the adhesion of rubber solutions to various substances canbe changed by incorporating relatively small amounts of the novelcomposition in the rubber. The elfect is highly specific to theparticular metal-acid complex and to the alcohol. Thus the use of onealcohol may increase the degree of adhesion of say a rubber adhesive toa given surface while the use of another alcohol may decrease theadhesiveness, all other components of the system remaining the same.

Again, by compounding the novel compositions into solid articles, e.g.of rubber, polyvinyl chloride, polyvinylidene chloride, polyethylene andpolypropylene, the adhesiveness of such objects to each other and tovarious conventional adhesives can be controlled.

The high molecular weight organic materials with which the presentcompositions are useful may include virtually any organic materialhaving a molecular Weight over say 10,000. Polymers of all types may betreated, particular elastomeric substances, and the roll of possiblematerials includes rubbers of all types, both natural and synthetic,synthetic resins including polyvinyl chloride, polyvinyl acetate,acrylic polymers such as polymethyl methacrylate, polyacrylonitrile,polystyrene, polyalkylenes such as polyethylene and polypropylene,cellulose, cellulose derivatives such as nitrocellulose and celluloseacetate, silicones, and waxes.

The mechanism by which the organo-metal compositions operate on thesurface characteristics of high molecular weight organic materials isnot known. However, it is theorized that the compositions have a headand tail structure in which the head and tail have markedly differentproperties. Depending on the nature of the material into which the novelcomposition is incorporated, either the head or the tail will appear onthe surface, thus aflecting the surface properties.

The amount of the novel composition which is incorporated in the highmolecular weight organic material may vary widely depending on thecomposition, the nature of the high molecular weight material and theeffect desired. In general it can be said that appreciable effects 13can be observed with as little as A of the composition (based on theweight of the material to which the composition is added). In general,not more than say of the composition will be added, again based on theweight of high molecular weight material.

The technique used to add the novel compositions to the high molecularWeight material will vary greatly. One convenient technique has been todilute the composition to a rather low concentration of solids (say 2%solids) with a solvent which will be taken up by the material and thenadd this solution to the material. Other convenient techniques may beused.

This aspect of the invention will be further described with reference tothe following specific examples:

Example 27 The following polymer solutions are made up of:

(a) a-solution of 10.6% prime natural rubber in toluene;

(b) a solution of 25.7% polyisobutylene (Enjay Butyl 268) in toluene;

(c) a solution of a hot process styrenebutadiene polymer (Plioflex 1006)in toluene;

(d) a 22.5% solution of a cold process styrenebutadiene (Pliofiex 1507)in toluene;

(e) a 20% solution of a butadiene-acrylobutrile rubber prepared by thecold process (Chemigum M-600) in toluene;

(f) a 25.7 solution of polychloroprene (Neoprene WRT) in toluene;

(g) a solution of polyvinyl methyl ether in toluene;

(h) a solution of 45 g. of polyisoprene (Shell 305) in 405 g. toluene;

(i) 60 g. cis-4 polybutadiene in 240 g. toluene.

To solution (b) a sufiicient quantity of various metalorganocompositions is added to give'2% metal-organo solids on polymer solids.Super calendared 40 pound 24 x 36 unbleached vegetable parchment iscoated with the test solution, using an iron bar to make the drawdowns.The sheets are air dried at room temperature for 24 hours, weighed andtested.

In a first series of tests a 1 wide strip of the coated parchment islaid on a piece of uncoated parchment and a piece of cardboard the samesize is laid on top. A pressure of 400 p.s.i. is then applied at roomtemperature for two minutes. The stripping force required to separatethe two surfaces in a 180 peelback is measured in a tensile tester.

In a second test procedure two coated strips of the same size (1" wide)are laid face to face with the coated surfaces in contact. Light fingerpressure, just enough to bring the surfaces into contact, is applied andthe stripping force at 180 peelback is determined within 2 minutes.

The metal organo solutions used in this series of tests are:

(A) Docosanato-chromic chloride-n amyl alcohol prepared in accordancewith Example 2.

(B) Docosanato-chromic chloride-ethanol prepared in accordance withExample 2.

(C) Docosanato-chromic chloride-stearyl alcohol prepared according toExample 2.

(D) Docosanato-chromic chloride-oleyl alcohol prepared according toExample 2.

(E) Docosanato-chromic chloride-2-methyl-3-butyn-2-ol prepared accordingto Example 2.

(F) Sorbato-chromic chloride-n-pentanol prepared accord ing to Example6.

(G) Sorbato-chromic chloride-terbutanol prepared according to Example 6.

(H) Valerato-chromic chloride-n-pentanol prepared according to Example6.

(I) Valerato chromic chloride-terbutanol prepared according to Example6.

(I) Isovalerato-chrornic chloride-n-pentanol prepared according toExample 6.

14 (K) Isovalerato-chromic chloride-terbutanol prepared according toExample 6. The results of the tests are tabulated in Table VII below:

TABLE VII I Coating Stripping force Composltlon, wt., Metal-organo wt.percent lbs On parch- Self adheeomposition added ream ment (g.) sion(g.)

None 12 159 491 12. 9 11 327 362 17. 9 14 329 318 32 325 350 13. 1 36 5014. 2 33 50 60 37. 8 44 425 250 11.2 35 400 75 16. 8 33 160 60 12. 4 32744 391 15. 9 30 585 275 10.0 29 200 150 12. 5 27 415 715 The procedurejust described is then repeated with various polymer solutions otherthan polyisobutylene (solution b). In each case the proportion ofmetal-organo composition added is such as to give 2% metal-organo solidson polymer solids. The results are tabulated in Table VIII below.

TABLE VIII Organo-metal composition Stripping force Coating Compo- Wt.,Weight, On pareh- Self adhesition percent lbs/ream ment (g.) sion (g.)

Polymer a None 7 102 12. 9 5 87 17. 9 4 164 6 155 9 3G 27 14 42 28 12585 533 11 135 44 11 198 88 9 655 1, 290 12. 9 12 52 62 17. 9 15 82 1836 840 1,030 12.9 8 570 1, 330 17.9 4 206 331 2 12 129 12.9 2 38 188 17.9 3 12 225 .1 5 0 30 12.9 2 0 0 11 35 580 12.9 8 50 30 Example 28Sufiicient docosanato-chromic chloride-n-pentanol and ethanol solutions(solutions A and B) are added to a 25% dimethylpolysiloxane (Dow-Corning271)-toluene solution to give 2% metal-organo solids on polymer solids.Parchment is coatedas in Example 27. To determine stripping force onparchment a one inch wide strip of the coated parchment is laid onuncoated parchment and light pressure, only enough to secure contact isapplied along with heat (104 C. for 2 minutes). The assembly is cooledto room temperature and stripping force is measured at peelback. Asimilar procedure is used to determine self adhesion except that twocoated sheets are used. Results are tabulated in Table IX below.

Metal organo solution A, identified above in Example 27, is added tovarious polymer solutions in proportions such as to give 2% ofmetal-organic solids on the Weight of polymer solids. The solutions arecoated on smooth, super-calendered unbleached vegetable parchment(Paterson Parchment Paper Company Durapak -735) and allowed to air dryat room temperature for 24 hours. The

polymer solutions used are as follows:

(j) 90 g. poly-n-butyl methacryllate (Lucite 44) dissolved in 270 g.toluene.

(k) 100 g. polystyrene (Lustrex HF-l 1) in 270 g. toluene.

(l) g. cellulose acetate butyrate (Eastman FAB 500-5) in 270 g.isopropyl acetate.

(m) 105 g. cellulose acetate (Eastman E 398-3) in 215 g.

acetone.

(n) 265 g. nitrocellulose (Hercules /2 sec.) in 225 g.

acetone.

TABLE X Stripping force Compo- Coating Metal-organo sition, Percentweight, On parch- Self adheeomposition wt. added lbs/ream ment (g.) sion(g.)

1 Tears 1 160 1 0n super-calendered Kraft paper.

Example 30 A study is conducted to ascertain the effect of directaddition of certain metal-organo compositions in suitable solvents tovarious types of pressure sensitive adhesives. The procedure is to weighout 50 g. of the adhesive under test and to this adhesive add suflicientmetal-organo composition in solution to equal 2 percent metal-organosolids on dry adhesive solids. The adhesive mixtures are coated ontounbleached super-calendered vegetable parchment and allowed to air dryat room temperature for 24 hours. The amount of adhesive coating weightis determined by weighing the coated sheet and comparing with the weightof an uncoated sheet of the same size.

In a first test procedure a one inch wide strip of coated parchment fiveinches long is laid on a sheet of supercalendared vegetable parchmentand light finger pressure applied, just enough to insure contact betweenthe surfaces. Within two minutes the stripping force required toseparate the two surfaces in an 180 degree peelback test is measured inthe tensile tester.

In a second test procedure, two coated surfaces are brought into contactwith light finger pressure. The stripping force on 180 degree peelbackis determined within two minutes.

Testing temperature for both series is 24 C.

Results are secured for both the plain adhesive and for the sameadhesive with 2% complex solids on adhesive solids added and therelative stripping force for the metalorgano containing adhesives isreported as percent of the force for the plain adhesive.

The adhesives used are Rubber and Asbestos Corporations P561, describedas a synthetic rubber-resin type, Rubber and Asbestos P538, a pigmentednatural rubber type, and Rubber and Asbestos P578, described as asynthetic resin type.

The metal-organo solutions used are in some cases those identified inExample 27 above. However, there are also used the following solutions:

L) A solution of linoleato-chromic chloride-isooctanol prepared asdescribed in Example 6.

Tears 133 (M) A solution of IO-undecanato chromic chloride-isooctanolprepared by fusing 21.3 g. of chromic chloride hexahydrate with 9.2 g.IO-undecanoic acid for 1 hour at 150 C. and refluxing the resultingsolid for one hour with g. of isooctanol. The cooled, filtered solutioncontains 15% solids.

(N) A solution of octanato-chromic chloride-isooctanol prepared byfusing 21.3 g. of chromic chloride hexahydrate with 11.5 g. ofN-octanoic acid for 1 hour at 150 C. and refluxing the product with 105g. of isooctanol for one hour. The cooled, filtered solution contains16% solids.

The results obtained are given in Table XI below:

TABLE XI Relative stripping force On pareh- Self adhe- Adhesive ment,percent sion, percent Metal-organo composition:

B R and A p561 60 29 A RandApSSl... 17 111 L.. R and A p561- 76 89 M Rand A p561... 78 105 N. RandAp561 63 83 B R and A p578 111 A. R and Ap578 157 171 L R and A p578 105 M RandAp578 115 N R and A p578 67 147 BR and A p538- 79 111 A- R and A p538 159 91 L R and A p538..- 23 65 M. Rand A p538 91 70 N. RandAp538 23 51 In these experiments the proportionsof compositions B, A, L, M and N added to the adhesive are 17.9%, 12.9%,12.9%, 12.9% and 12.4%, respectively.

These data clearly show that addition of alcohol modified complexes ofdecosanato chromic chloride, octanato chromic chloride, linoleatochromic chloride, and 10-undecanato chromic chloride influence theself-adhesion characteristics and the bond to cellulose of threewellknown types of pressure sensitive adhesives. The data shows that thetype of alcohol has an effect on the results observed.

Example 31 The eifect of the docosanato-chromicchloride-rosinisopropanol-hexane and octanato-chromicchloride-resinisopropanol-hexane solutions made in Examples 8 and 11 anda linoleato-resin-pentanol-hexane solution prepared in a similar manner,on the adhesive qualities of butyl and butadiene-styrene rubbersolutions is investigated. The metal-organo solutions are identifiedbelow as O, P, and Q respectively.

Solutions are made up by dissolving 90 g. of butyl rubber (Enjay 268)and 60 g. of styrene-butadiene rubber (Ameripol 1500) in 260 and 210 g.of toluene, respectively. To portions of each of these solutions smallquantities of the metal-organo solutions are then added, the amountbeing sufiicient to give 2% organo-metal solids on rubber solids.

In a first series of tests, the solutions are coated on to smooth,super-calendared, unbleached vegetable parchment (Paterson ParchmentPaper Company Durapak 40- 73a) and allowed to air dry at roomtemperature for 24 hours. Strips 1" x 5" are cut and pressed on the sameuncoated paper with a pressure of 40 p.s.i. for two min utes at roomtemperature. The strip is then peeled in a tensile tester with rollback.

In a second self adhesion series, two coated 1" x 5" strips are laidface to face using light finger pressure and immediately stripped in thetensile tester using 180 rollback.

17 The results of these tests are tabulated in Table XII below.

TABLE XII Metal-organo composition Uncoated Self- Wt. Lbs. of parchmentadhesive Compopercent coating stripping stripping Rubber sition addedperream force (g.) force (g.)

Butyl None 12 160 490 D O 8. 6 13 442 390 10.2 388 640 8.0 15 405 510 442 110 Example 32 The coated strips of Example 31 are applied to varioussurfaces and the stripping force measured. Results are tabulated below(Table XIII):

The data clearly shows that addition of rosin modified docosanatochromic chloride, rosin modified octanato chromic chloride, and rosinmodified linoleato chromic chloride all improve the adhesion of butylrubber and butadiene rubber to cellulose. Self adhesion is improveddrastically in the case of styrene-butadiene rubber. Bond strength tovarious surfaces other than cellulose is also greatly increased by theaddition of the novel composition.

Example 33 A solution containing g. gum resin, 100 g. hexane and 10 g.isopropanol is made up and added to a butyl rubber-toluene solutionprepared as described in Example 31 to give 2% rosin on rubber. Theadhesive eifect of this is then compared with a like solution to whichorganometal solution 0 (Example 31) has been added. Results aretabulated in Table XIV below.

These figures show that the rosin-docosanato chromic chlorideisopropanol-hexane solution is considerably more eifective than rosin inimproving the bond of butyl rubber to cellulose.

Example 34 A series of experiments is run testing the effect of addingsolutions 0, R, and Q of Example 31 to various polymeric solutions. Incertain cases, the polymeric solutions are those described in Examples27 and 29 above; in other instances the following solutions were added:

(0) 234 g. dimethylpolysiloxane (Dow Corning 271) in 117 g. toluene.

(p) 150 g. polyvinylacetate solution (Elvacet 60-05) in 2 10 g.methanol.

Solutions 0, P and Q are added] to each of these polymer solutions inproportions of 8.6%, 10.2% and 8.0%, respectively. The resultingcombined solutions are then applied to unbleached super-calendaredparchment as described in Example 28. In the case of polymer solutions,8, f, g, h, and q the stripping force is then determined as described inExample 28. The results of these tests are tabulated in Table XV below.

TABLE XV Stripping force (g.)

organo metal L bs., coat- On pareh- Self composition ing/ream mentadhesion In the case of polymer solutions j and 0, a coated sheet of theparchment is bonded to an uncoated sheet and also to another similarlycoated sheet by exposure to a temperature of 104 C. for 2 minutes usinglight contact pressure only, in a Williams sheet drier. The samples arethen cooled and the stripping force (180 peelback) determined. Theresults are tabulated in Table XVI below.

In the case of polymer solutions k, l, and m the sheets of coated paperare wet with the solvent originally used to make the polymer solution,using a cotton swab. The wet sheets are applied either to a sheet ofuncoated paper or to a sheet of coated paper which has not been rewetwith solvent (self adhesion). Heat is then applied on a Williams sheetdrier for 2 minutes at 104 C. with light pressure. Stripping force ismeasured as before. The results are given in Table XVII below.

TABLE XVII Stripping force Metal-organo Lbs. coat- On parch- Selfahdecomposition ing/ream merit (g.) sion (g) 1 9 Example 35 TABLE XVIIIWood rosin composition Tali oil rosin composition Concen- Strippingforce (g.) Concen- Stripping force (g.)

tration tration Wt. On parch- Self Wt. On parch- Sell percent mentadhesion percent ment adhesion Example 36 Varying amounts of certainmetal organo compositions prepared in preceding examples are added toportions of the polyisobutadiene solution whose preparation is describedin Example 35. The stripping force to parchment andself adhesion arethen determined as in Example 31.

20 Example 38 Experiments are conducted to ascertain the effect ofdirect addition of rosin modified compositions in suitable solvents tovarious pressure sensitive adhesives. The procedure is to weigh out 50g. of the adhesive to be tested. To the adhesive, sufficientmetal-organic composition is added to equal 2% metal-organo solids ondry adhesive solids. The adhesive mixtures are coated onto unbleachedsuper-calendered vegetable parchment and allowed to air dry at roomtemperature for 24 hours. The amount of adhesive coating weight isdetermined by weighing the coated sheet and comparing it with the weightof an uncoated sheet of the same size.

In a first series of tests, a one inch wide strip of coated parchmentfive inches long is laid on a sheet of unbleached super-calendaredvegetable parchment and light finger pressure applied, just enough toinsure contact between the surfaces. Within two minutes the strippingforce required to separate the two surfaces in a 180 degree peelback ismeasured on a tensile tester.

In a second test series, two coated strips of the same size were laidface to face with the two coated surfaces contacting each other. Lightfinger pressure to insure good contact is applied. The stripping forcein 180 degree peelback is determined within two minutes.

The testing temperature in both test series is 24 C. The adhesives usedare Rubber and Asbestos Corporations P561, described as a syntheticrubber-rosin type.

The e ult e reported i T bl XIX b l 30 Rubber and Asbestos P538, apigmented natural rubber TABLE XIX Prep. of Stripping force (g.)

composition Wt. percent Coating, Acid used in Metaldescribed ofcomposilbs. 011 parch- S cli organo composition in exampletion addedream ment adhesion Soribc 18 8. 5 33 160 419 Hydroxy stearic.- 20 J. 536 65 185 Valerc..--.. 21 9. 8 33 255 200 Isovaleric. 22 8. 1 32 255 230Isodecanoic. 23 8. 9 29 165 265 Crotonc... 19 9. 27 140 295 Octanoic 127. 30 210 240 Example 37 type, and Rubber and Asbestos P578, a syntheticrosin The chromic chloride-rosin-isopropanol composition of type-Example 16 is added, in a proportion of 8%, to the butylrubber andbutadiene-styrene rubber solutions of Example 31, to the polyisoprenepolyisoprene (h) and polybutadiene (i) solutions of Example 27, to thedimethylpolysiloxane (0) solution of Example 34 and to the celluloseacetate butyrate (l) and polystyrene (k) solutions of Example 28. Thecomposite solutions are then applied to parchment as before and driedovernight. Stripping force with respect to uncoated parchment and selfadhesion are then determined as in Example 31. The results are givenbelow in Table XX.

TABLE XX.

Metalorganol Stripping force (g.) composition Lbs. coat- On parch- SelfPolymer added ing/ream ment adhesion Pure butyl rubber No 6 155 675 Yes.600 690 Styrene-butadicne rubber. No 6 206 155 Yes-.... 14 220 40Polyisoprene No 5 0 Yes. 2 0 15 Polybutadiene N0 11 580 Yes..... 14 165265 Cellulose-acetate butyrate No 12 Z 120 2 80 es... 18 2 100 Z 120Polystryene No 5 2 90 2 75 Yes-. 8 2 75 2 170 Dimethylpolysiloxane No 2l 25 1 305 Yes- 2 l 75 l Bonded with heat only. 2 Coating molstened withso vent and hea pp e The metal-organo compostions used are solutions 0and P, i.e. the docosanato-chromic chloride-rosin-isopropanolhexanesolution of Example 8 and the octanatochromicchloride-isopropanol-hexane solution of Example 11.

The results for the compounded adhesive are reported in Table XXI asrelative stripping force, i.e. percent of the value for the pureadhesive, at equal coating weight.

TABLE XXI Relative stripping force Metal- Wt. On parch- Self organopercent inent, adhesion. lbs. coat comp. added Adhesive percent percentting/ream 8.6 R and A 13561. 111 114 10.2 R and A p561. 86 17 8. 6 R andA p578. 143 143 11 10. 2 R and A p538. 139 61 5 TABLE XXII Relativestripping force On parch- Self Cone. of metal-organo solids, percentmerit, adhesion, Lbs. coatby weight of adhesive solids percent percentting/ream 138 148 11 125 150 13 138 176 11 143 143 11 158 8 These datashow that 1.3% rosin modified octanato chromic chloride-isopropanolcomposition in hexane solution was sufficient to eifect a markedimprovement in the adhesiveness of Rubber and Asbestos p578 and thatadditional amounts, up to ten times as much, are of very littleadditional benefit.

Example 40 One hundred grams of medium density polyethylene (MonsantoMPE 2203) are mixed with four hundred grams of toluene, and the mixtureis gradually heated, with considerable agitation, to just below theboiling point of toluene. Under these conditions, the polyethylenegradually dissolves to form a viscous solution. To fifty gram portionsof this solution, various metal-organo compositions are added withagitation, making sure that the temperature is kept just below theboiling point of the toluene. Good compatibility is noted in all cases.

Two of the metal-organo compositions added are those designated earlieras solutions F and P. In addition to solutions F and P, solutions R, S,T, U, V, W and X are used.

Composition R is a sorbato-chromic chloride-isoamyl alcohol compositionmade by substituting isoamyl alcohol for the isopropanol and n-amylalcohol of Example 18. Composition S is a docosanato-chromicchloride-rosinisopropanol-hexane composition whose manufacture isdescribed in Example 8. Composition T is similar to thecrotonato-chromic chloride-gum rosin-isoamyl alcohol composition whosemanufacture is described in Example 19, isoamylalcohol being substitutedfor isopropanol. Composition U is the amino-acetato-chromicchloride-rosin-isopropanol composition whose manufacture is described inExample 24. Composition V is the amino-acetato-chromiumchloride-rosin-butanol composition of Example 25, Composition W in the2-amino-octanato chromic chloriderosin-n-butanol composition of Example26. Composition X is the 1Z-hydroxy-stearato-chromicchloride-rosin-isopropanol hexane composition of Example 20.

A piece of brown super-calendered vegetable parchment is placed on anelectrically heated hot plate and a previously heated iron rod placed atone end. A portion of the test solution is poured out and the iron roddrawn down across the parchment to form a continuous film of coating.The sheet is left on the hot plate until the solvent has evaporated andis then removed.

As a testing procedure, coated 1" x 5" strips are placed face to faceand then heated for two minutes at 115 C., using light applicationpressure, just enough to keep the surface in firm contact. The stripsare fused together by this procedure and are cooled and stripped in atensile strength tester, using 180 degree peelback. This is recorded asself adhesion. The same procedure is repeated, except that a strip ofcoated parchment is placed in contact with a strip of plainsuper-calendared unbleached vegetable parchment. Results are reported asbond to parchment. Parchment is used as the test medium because the pooradhesion of polyethylene for this surface is well known.

The results are given in Table XXIII as follows:

The following examples disclose incorporating chromium complexes of theinvention in various high molecular weight organic materials to modifythe surface characteristics of these materials. The ability of variousadhesives to adhere to these modified organic materials is described.

Example 41 1" x 5" strips of pressure sensitive adhesive tape (MinnesotaMining and Mfg. Co. No. 202) are applied, under a pressure of 400 p.s.i.for 2 minutes at room temperature, to modified polyethylene coated brownsuper-calendared vegetable parchment. The vegetable parchment sheets arecoated with certain modified polyethylene solutions according to theprocedure described in Example 40. The polyethylene solution used forcoating is described in Example 40 and is modified by the addition ofmetal-organo compositions F, T, W and X.

The stripping force required to strip the tape from the modifiedpolyethylene at degree peelback is measured 1in a standard tensiletester. The results are tabulated be- TABLE XXIV Stripping Wt. percentof force on composition parchment (g.)

Metalrliorgano composition:

Example 42 Pieces of brown super-calendered vegetable parchment arecoated with solutions of polyethylene containing metal-orgauocompositions, S, T and W, according to the procedure described inExample 40.

The modified polyethylene films on parchment are then coated withcertain polymer composiitons including polymer solution b, and a 22.2%by weight, solution of styrene-butadiene (Ameripol 1500) in toluene,hereafter designated as polymer solution q. The polymer compositions arecoated over various modified polyethylene surfaces and the coating isallowed to dry for a period ranging from three to four days at roomtemperature. Two inch Wide strips of the coated parchment are laid faceto face with the coated surfaces contacting each other. A pressure of400 p.s.i. is then applied to the strips at room temperature for twominutes. The stripping force required to separate the polymercomposition from the modified polyethylene in a 180 peelback is measuredin a tensile tester. The results are tabulated below:

Example 43 A mixture of polyvinyl chloride (B. F. Goodrich Geon 101) anddioctyl phthalate plasticizer (B. F. Goodrich G P 261) is prepared bydispersing 240 grams of polyvinyl chloride in a solution comprising 160grams of the plasticizer and 10 grams of hexane. To this dispersion 8%by weight, based on plastisol solids, of metal-organo compositions L, S,T, V, W and octanato chromic chloriderosin-isopropanol-n-hexanol,hereafter designated Y, prepared according to the procedure described inExample 11 except that n-hexanol is substituted for hexane, are added.

The dispersions are then coated on kraft paper and fused for two minutesat 193 C. The modified polyvinyl chloride film on kraft paper is thencoated with certain polymer compositions including polymer solutions 12and q. The polymer compositions are coated over the various modifiedsurfaces and the coating is allowed to air-dry for a period ranging fromthree to four days at room temperature. One inch wide strips of thecoated paper are cut and the two polymer surfaces brought into contact.A pressure of 400 p.s.i. is then applied to the strips at roomtemperature for two minutes. The stripping force required to separatethe polymer composition from the modified polyvinyl chloride in a 180peelback is measured in a tensile tester. The results are tabulatedbelow:

1 8% complex on plastisol solids.

The results set forth in Examples 40 to 43 show that the addition of themetal-organo compositions of the invention to various high molecularweight organic materials such as polyvinyl chloride, modifies certainproperties of these organic materials significantly. For example, theability of other substances, including pressure sensitive adhesives andpolymeric materials such as various rubber compositions to adhere tometal-organo modified polymer films is illustrated.

Considerable modification is possible in the variation of details inpracticing the present invention without departing from the scopethereof.

I claim:

1. A mixture of (a) a polymeric organic material having a molecularweight over 10,000 selected from the group consisting of natural rubber,polyisobutylene, styrene-butadiene copolymers, acrylonitrile-butadienecopolymers, polychloroprene, polyvinyl methyl ether, polyisoprene,polybutadiene, poly-n-butylmethyacrylate, polystyrene, celluloseacetate-butyrate, cellulose acetate, nitrocellulose,dimethylpolysiloxane, polyvinylacetate, polyethylene andpolyvinylchloride, and (b) from A to 10%, by weight, based on the weightof (a) of a water insoluble, organo-chromium complex comprising a fusedchromium-monocarboxylic organic acid coordination compound, in which theratio of chromium atoms to carboxylic acid groups is from about 1:4 toabout 10:1 prepared by melting together a trivalent chromium salt and amonocarboxylic organic acid having from 2 to 22 carbon atoms, bonded bycoordination through the chromium to an alcohol selected from the groupconsisting of n-butanol and aliphatic alcohols having from 5 to 18carbon atoms, the proportion of said alcohol to said coordination com-Pound being from about 1000:1 to about,0.l 1.

2. The composition of claim 1 wherein said monocarboxylic acid isselected from the group consisting of butyric, valeric, isovaleric,caproic, octanoic, undecanoic, isodecanoic, lauric, myristic, palmitic,stearic, arachidic, docosanoic, a-methylcaproic, a-octyl caproic,,B-ethyl stearic, methyacrylic, crotonic, sorbic, linoleic, geranic,oleic, palmitolic, eicosinic, aminoacetic, Z-aminooctanoic,u-chlorovaleric, 5,,8-dibromocaproic, ,B-hydroxy pelargonic, a-aminoundecanoic and 12-hydroxy stearic acids; and wherein said aliphaticalcohol is selected from the group consisting of n-butyl alcohol, n-amylalcohol, nhexyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol,isooctyl alcohol, 3 isopropyl 4 methyl-3-hexanol, 3-methyl-3-butyn-2-ol, 1-penten-3-ol, 4-penten-3-ol, S-hexen- 3-01 andpinacol.

3. The composition of claim 1 wherein said monocarboxylic organic acidis selected from the group consisting of:

and wherein said coordination compound is also bounded by coordinationthrough the chromium to rosin in an amount of between about 0.1 andabout 2 parts of rosin per part of complex.

4. The composition of claim 3 wherein said monocarboxylic acid isselected from the group consisting of butyric, valeric, isovaleric,caproic, octanoic, undecanoic, isodecanoic, lauric, myristic, palmitic,stearic, arachidic, methacrylic, crotonic, sorbic, linoleic, geranic,oleic, palmitolic, eicosonic, aminoacetic, Z-aminooctanoic,achlorovaleric, fl fi-dibromocaproic, fl-hydroxy pelargonic, a-aminoundecanoic and 12-hydroxy stearic acids; and wherein said alcohol isselected from the group consisting of n-butyl alcohol, n-amyl alcohol,n-hexyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, isooctylalcohol, 3- isopropyl 4 methyl-3-hexanol, 3-methyl-3-butyn-2-ol,1-penten'3-ol, 4-penten-3-ol, 5-hexen-3-ol and pinacol.

5. A mixture of (a) a polymeric organic material having a molecularweight over 10,000 selected from the group consisting of natural rubber,polyisobutylene, styrene-butadiene copolymers, acrylonitrlle-butadienecopolymers, polychloroprene, polyvinyl methyl ether, polyisoprene,polybutadiene, poly-n-butylmethylacrylate, polystyrene, celluloseacetate-butyrate, cellulose acetate, nitrocellulose,dimethylpolysiloxane, polyvinylacetate, polyethylene andpolyvinylchloride, and (b) from about A to 10%, by weight, based on theweight of (a) of a water insoluble, organo-chromium complex comprising afused chromium-monocarboxylic organic acid coordination compound, inwhich the ratio of chromium atoms to carboxylic acid groups is fromabout 1:4 to about 10:1, prepared by melting together a trivalentchromium salt, rosin and a monocarboxylic organic acid having from 2 to22 carbon atoms bonded by coordination through the chromium to analiphatic alcohol selected from the group consisting of n-butanol andaliphatic alcohols having from 5 to 18 carbon atoms, the proportion ofsaid alcohol to said coordination compound being from about 1000:1 toabout 0.121 and the amount of rosin is between about 0.1 and about 2parts thereof per part of complex.

6. The composition of claim 5 wherein said monocarboxylic acid isselected from the group consisting of butyric, valeric, isovaleric,caproic, octanoic, undecanoic, isodecanoic, lauric, myristic, palmitic,stearic, arachidic, methacrylic, crotonic, sorbic, linoleic, geranic,oleic, palmitolic eicosonic, aminoacetic, Z-aminooctanoic,tit-chlorovaleric, 3,,B-dibromocaproic, ,B-hydroxy pelargonic, f5-

amino undecanoic and 12-hydr0xy stearic acids; and wherein said alcoholis selected from the group consisting of n-butyl alcohol, n-amylalcohol, n-hexyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol,isooctyl alcohol, 3-isopropyl-4-methyl-3-hexanol, 3-methyl-3-butyn-2-ol,1- penten-3-ol, 4-penten-3-ol, 5-hexen-3-ol and pinacol.

7. The composition of claim 5 wherein said monocarboxylic acid isselected from the group consisting of:

(1) saturated straight chain acids,

(2) saturated branches chain acids,

(3) unsaturated straight chain acids,

(4) unsaturated branched chain acids, and

(5) aliphatic acids containing functional groups, in addition to thecarboxylic group, selected from the group consisting of halogen,hydroxyl and amino.

References Cited UNITED STATES PATENTS 12/1934 Harrington 260-23.76/1945 Pragoff, Jr. 260-755 8/1959 Rouse, Jr. et al. 106-173 4/1966Dipner 260-921 8/1966 Matlack 260-4575 4/1968 Louden 260-103 PrimaryExaminer U.S. C1. XLR.

Patent No.

Inventor(s) Column 11,

Column 14,

Column 16,

Column 16,

Column 20,

Column 2 (SEAL) Atteat:

EDWARD M.FIETCHER,JR. Attesting Officer UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Dated December 15, 1970 William C. London Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 5, line 55, "191.1 g" should read 19. l g

line 28, "23.3575" should read 23.5%

line 67, "279" should read 270 line 40, "decosanato" should readdocosanato lines 50 8c 52, "resin" should read rosin line 60, Theheading "Example 39" omitted from pa line 28, "bounded" should readbonded Signed and sealed this 15th day of June 1 971 WILLIAM E.SGHUYLER, JR Commissioner of Patents ran I-IA 15-- n im.

